Motor fuel treating process and products obtained thereby



Patented Nov. 24 1936 UNITED STATES PATENT- OFFICE MOTOR FUEL TREATING PROCESS AND PRODUCTS OBTAINED THERE-BY Thomas W. Bartram. Nitro, W. Va., assignor, by

mesne assignments. to

Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawlng. Application "April I; 1932, Serial No. 603,903

lilclaims.

The present invention relates to a composition as a circulating medium in all heating systems, and

the like. One object of the present invention is to provide a new treated oil composition possessing desirable stabilizing properties.

Another object of the present invention is to provide a new mineral oil product possessing improved properties particularly for use as a fuel for internal combustion engines. The treating means and special compositions disclosed herein are likewise adaptable for use as a transformer oil, as a lubricating means, as a heat circulating medium and analogous uses wherein it is desirable that an improved and satisfactorily stable mineral 011 product be employed.

It is well known that combustible liquids derived from mineral oils before the usual refining processes, frequently and in some cases invariably, contain a proportion of ingredients which give rise to resin formation. This is particularly the case with various fractions of oils produced by different refining and treating means from various crude oils. Immediately and for a short time after distillation, such unrefined motor fuel, for example cracked gasoline, may be comparatively free from non-volatile resinous matter, but on storage or when used in internal combustion engines give rise to resinous material. The resinous material on storage may either remain dissolved in the liquid, or in certain cases be partially separated.

A further object of the present invention is to substantially prevent or greatly reduce the resin 'formation in such liquids, thus rendering it possible to store them for substantially long periods of time without deterioration and to use them satisfactorily as fuels in internal combustion engines, thus avoiding or considerably reducing refining losses.

It has been recognized that if the above mentioned fuels could be treated in some manner which would prevent resin formation there would be a great advantage in using such fuel which has been refined as little as possible in view of the economy of utilizing the whole of the unsaturated constituents and also because these constituents possess valuable anti-knock properties.

According to the present invention, a new oil composition has been obtained which has particularly desirable characteristics and which is resistant to the formation of gummy and resinous .placeisin deposits. More particularly, the present invention relates to the incorporation in a mineral oil or material derived therefrom, of a suitable material which greatly inhibits the formation of resin, gum. and like deposits.

The class of materials which have been found to possess the desirable qualities set forth in that small proportions thereof when incorporated in a relatively unstable oil product, for example, gasoline, materially increase the stability thereof, comprise a class of materials possessing a ring structure of More particularly the present invention relates to the stabilization of unstable oil products, for example, gasoline, by incorporating therein a small proportion of an oxazine possessing the above described ring structure.

In order to test the gum inhibiting properties of the preferred class of materials the following procedure, which is essentially that described by E. B. Hunn, H. G. M. Fischer and A. J. in the Society of Automotive Engineers Journal, vol. 26, #1 (1930), pages 32 and 33, was employed.

Into an Emerson coal calorimeter bomb having a capacity of 500 cc., 2. small glass open vessel having a capacity of substantially 150 cc., was placed, which contained cc. of an untreated unstable gasoline, such as, for example, a gasoline known as cracking coil distillate, to which had been added a small proportion of one of the preferred class of materials which may be called gum inhibitors. The lid was then placed tightly on the bomb. Substantially one hundred pounds pressure of omen was then introduced by means of a delivery tube, after which said delivery tube was closed by means of a suitable valve. The bomb was then connected by means of adelivery tube with a pressure gauge having a range between 0 to 200# and having an accurate scale from 10th after which it was heated preferably by immersing it in a hot water bath maintained at 97 to 98 C. and maintained at said temperature so long as there was no appreciable drop in pressure as indicated by the pressure gauge. A drop in pressure indicates a reaction between the oxy e and the imstable portion of the gasoline. The period of time elapsing before this reaction takes 'cative of the stability of the gasoline.

For the special type of gasoline mentioned, that is the gasoline known as cracking coil distillate'i,

.2 v the period of.'stability as hereinafter employed is thetime in minutes from the time of the immersion of the bomb in the bath maintained at a temperature of 97-98 C. until there is a drop in pressure on the pressure gauge of pounds per square inch.

As one method of operating the present invention' one of the preferred materials, for example 30 m. g. of phenoxazine, possessing the structural formula of was dissolved in 100 c. c. of unstable gasoline, for example cracking coil distillate and a test carried out in the manner hereinbefore described. The period of stability or in other words the period of time from the immersing of the bomb containing the gasoline in the liquid bath maintained at a. temperature of 97-98" C. until a drop in pressure of five pounds per square inch resulted,- was 1500 minutes.

A test carried out in an identical manner with .that given above, with the exception that no inhibitor was incorporated in the unstable gasoline, was 70 minutes. g

It is .thus shown that the preferred class of compounds, for example phenoxazine possesses marked stabilization properties, when incorporated in an unstable oil product, for examplegasoline.

If convenient or desirable, if the inhibitor to be added to the unstable 011 product, for example gasoline, is notreadily soluble therein, it may be dissolved in a solvent, for example isopropyl alcohol, benzol and other like solvents, fully miscible with said unstable oil product, and the solution of the inhibitor. thus prepared added thereto.

Other, oxazines possessing a ring structure of that have been incorporated in an unstable oil product, for example gasoline, and found to possess the characteristics of the preferred class of materials andfunction in the manner described comprise dinaphthoxazine, naphthophenoxazine, 4-nitro phenoxazine, G-nitro phenoxazine, 4-amino phenoxazine and G-amino phenoxazine.

-As further, examples of the preferred class of materials and falling within the scope of the present invention are the following: 3-methyl phenoxazine, 3,6-dimethyl phenoxazine, 2,4-dinitrophenoxaine,. phenanthroxazine, oxy-phenoxazone, phenyI-phenoxazime, naphthophenoxazone, phenoxazone, anilino-phenyl phenoxazime, phenonaphthoxazone, phenonaphthoxazime, hydroxyphenoxazime, triphendioxazine, methyl triphendioxazine, and morpholine and its analogues.

Other similar oil compositions designed for particularuses may be prepared in the manner described by merely'substituting the desired oil fraction or cut and adding the necessary quantity of gum inhibitor thereto. To produce the effect desired, a quantity of inhibitor equal to from approximately 0.001 to 0.05% of the weight of the oil is employed.

e Other ratios of the preferred class of materials than those hereinbefore set forth have been inwherein R is an aromatic radical consisting 0 carbon and hydrogen atoms only.

2. Gasoline produced by the cracking of i;.- leum oils containing as a gum inhibitor a all proportion of an oxazine of the formula i /N n wherein R is an aromatic radical consisting of carbon and hydrogen atoms only.

3. A process of stabilizing a cracked petroleum distillate fuel of the class which normally tends to form gummy material under normal conditions of handling and storage, which comprises adding thereto an unoxidized oxazine of the formula wherein R is an aryl radical.

4. A process of stabilizing a. cracked petroleum distillate fuel of the class which normally tends to form gummy material under normal conditions of handling and storage, which comprises adding thereto an unoxidized oxazine of the formula wherein R is an aromatic radical consisting of carbon and hydrogen atoms only.

5. A cracked hydrocarbon motor fuel of the type which tends to deteriorate on storage as evidenced by gum formation containing as a stabilizer thereof a small quantity of an oxazine of the formula wherein R. represents similar aromatic hydrocarbon radicals.

6. A cracked hydrocarbon motor fuel of the type which tends to deteriorate on storage as evidenced by gum formation containing as a stabilizer thereof a small quantity of phenoxazine.

7. A composition of matter comprising cracked gasoline of the type which tends to deteriorate on storage as evidenced by gum formation contaming as a. stabilizer thereof a small quantity of bilizer thereof a small quantity of a phenoxazine an oxazine of the formula free of dyeing properties for said gasoline.

n 9. A composition of matter comprising cracked I gasoline of the type which tends to deteriorate on storage as evidenced by gum formation contain- 5 ing as a stabilizer thereof a small quantity of a. 0 phenoxazine free of dyeing properties for said wherein R represents similar aromatic hydrocara ne- 10 bon radicals. l0. Gasoline produced by the cracking of pem 8. A cracked hydrocarbon motor fuel of the trolellm s containing 8 a 8 1 inhibitor 8- ma type which tends to deteriorate on storage as evi- Proportion of phenoxazinedenced by gum formation containing as a sta- THOMAS W. BARTRAM. 

